Azo compounds



Patented Feb, 28, 193$ UNITED STATES PATENT OFFICE 2.148.105 Azo COMPOUNDS ration of New York No Drawing. Application In Germany 11 Claims.

In accordance with the present invention azo compounds displaying a bactericidal action are obtainable by the manufacture of the compounds -0f the general formula: R N -N-R wherein R stands for a para-sulfamide or disulfamide substituted phenyl radical, and-R stands for a cyclic radical containing nitrogen in basic linkage, that is for a pyridine, quinoline or isoquinoline radical, which contains at least one further basic nitrogen atom in the form of an amino or alkylamino group, or contains at least one hyamino group of the sulfamide group may be a primary, secondary or tertiary amino group. It may, for instance, be substituted by saturated or unsaturated-alkyl or cycl'oalkyl groups, such as methyl, ethyl, allyl, butyl, isoamyl, cyclohexenyl, or by aralkyl groups, such as benzyl and phenylethyl. The two hydrogen atoms of the amifio r group may also be replaced by an alkylene group in which casethe nitrogen atom of the sulfamide group forms a hydrogenated heterocyclic ring systemv with the alkylene group, for instance, a pyrrolidyl or piperidyl ring. The new compounds may contain in the pyridine quinoline or isoquinoline radical besides the above specified characteristic groups other substituents, such as alkyl, halogen, hydroxyl, alkoxy, phenoxy and the nitro groupfibut free acid groups should notbe. present. The amino groups attached to theheterocyclic nucleus or the azo compounds may be substituted, for instance, by alkylgroups.

In accordance with the present invention the azo compounds of the kind'specified are obtainable by reacting upon afpyridine, quinoline or,

isoquinoline compound which contains-at least 40 one further nitrogen atom in the form or an amino or alkylamino group, or at least one hy-- droxylI group with a, parasulfamide or a disulramide diazo phenyl compound, whereby the heterocyclic components may be further substituted in the manner above indicated. 'The I680? tipn is advantageously carried out in the presence of water at a low temperature-say at about 20 C; or below. The azo compounds thus obtainable are colored powders which are insoluble in water but form, it they contain aminogroups, with mineral acids, such as hydrochloric, hydrobromic and sulfuric acid,'salts which dissolve more or less in water. tain attached to the heterocyclic nucleus hydroxyl 56 groups or contain a hydrogenatom at the amino droxyl group. In the new az'o compounds the The 9.20 compounds which con- July 2c, 1935, S8112? December 24, 1932 group or the sultamidegroup may also be dissolved in caustic alkalies; In view or their remarkable bactericidal action particularly against streptococci infections of warmblooded animals and new compounds have proved active in the] 5 treatment of infectious diseases.

The invention is further illustrated by the m1- lowing examples without being restricted thereto:

Example ,1-20-8 grams of the hydrochloride of 4-aminobenzenesulfonoamide are diazotized with 6.9 grams of sodium nitrite and treated with 10.9 grams of alpha-alpha'-diaminopyridine, dissolved in hydrochloric acid. Aiter some stirring sodium acetate is added and the mixture is left standing until the coupling reaction is complete. The solution is rendered alkaline by means of ammonia, filtered with suction, washed out and the free base after dissolving in methyl alcohol is converted with hydrochloric acid into the hydrochloride of 4-s1'1lfonoamidebenzeneazoalpha-alpha'-diaminopyridine which forms red brown prisms melting at 266 C. The compound is sparingly soluble in water, it is readily soluble in caustic alkalies with an orange coloration. It has the following iormula:

' norms-Oran at 35 0. The latter has the formula:;

nooHrcHpm.o,s N=N Hm -N NH:

Example 2.-2ll.8 grams or the hydrochloride 0! 4-aminobenzene.-sulionoamide are diazotized and mixed with 14.4 grams of fi-aminoquinollne,

dissolved in acetic acid. Aiter the, addition of .z'ui acetate the d' sulfono l d-amino uinoline oi the iormula aminoquinoline the base melting at 126 0., 6-

amino-d-m'ethylquinoline melting point of the hydrochloride above 300 C., '7-ethyl-aminoqulnoline, melting point of the hydrochloride 180 C., 7-butylaminoquinoline, melting point of the hydrochloride 178 0., 8-aminoquinoline, melting point of the hydrochloride 212 6., B-methyland S-methoxy-S-aminoquinoline, melting points of the hydrochlorides above 300 6., 5-aminoquinoline, melting point of the hydrochloride 192 C., G-h'ydroxy-B-aminoquinoline, melting point of the hydrochloride 370 C; (with decomposition), 5-amin0-isoquinoline, melting point of the hydrochloride 218 0.; further, the azo compounds of diazotized 4-aminobenzene-sulionodimethylamide and d-amincquinoline, melting point of the hydrochloride 258 C., the azo compound of 4-aminobenzenesulfonocyclohexylamide and G-aminoquinolin, melting point of the free base 270 C.-, and the sac compound of 4- 'Faminobenzene-suli'onopiperidide and G-aminoquinoline, melting point of the tree base 20 C.

The latter has thei'ormula:

Example 3.--20.8 grams 'of the hydrochloride of 4-amino-benzene-sulionoamide are diazotized in the customary manner and treated with 12.5

'grams oi 2.4-dihydroxy plcolinein excess dilute caustic soda lye. The 4-sulfonoamlde-benzeneazo=2.4-dihydroxypicol ine oi the'iormula:

, me on is obtained on the addition of acetic acid to the orange, red colored solutionas a yellow precipitate which after solution; with caustic soda lye and reprecipitation with acetic acid melts at alfove 300 C.

In an analogous manner-3'-5' disulionoamldebenzene-azo-2.4-dihydroxypicoline is obtained in the form of a yellow powder meltingabout 300 C. when starting with the 3'-5'-disulfonoamide-diazo benzene. It has the formula:

HnNOrB Hal-T018 N Example 4.2 0.8" grams of the thy act with 1%.5 grams or s-hydroxyquinoline in are cess dilute caustic alkali lye. From the deals solution the e-sulfonoamidebenzene-azo-8-hydroxy uinoline oi the formula:

precipitates on the addition of acetic acid as a dark brown crystalline powder which after re dissolving in caustic soda lye and reprecipitahon with acid melts at 234 6. I

a In an analogous manner there are obtained the 4'-sulfonoamide-benzene-azo-S-hydroxyqulnoline in the form of red brown crystals melting at 171 C. which dissolve in dilute caustic soda lye HzNOsB V with cherry red coloration; the e'-sulfonoamidebenzene-azo-S-hydroxyquinoline in light red crystals melting at 268 C.; the '-sulionoamidebenizene-azo-I-hydroxyquinoline as light red crystal powder melting at 228 6.; the ii'-sulfonoamide-benzene-azo 6 chloro 8 hydroxy qulnoline as dark brown crystal powder melting at 154 C. the '1'-sulfonoamide-benzene-azo- 5-methyl-8-hydroxyquino1ine as brick red crystal powder melting at 232 (3.; thet sulfonoamidebenzene-azo 8 methyl -5 -hydroxyquinollne as without departing from the spirit or'scope of the invention in its broadest aspects. Hence, we de side to cover all modifications and forms within the scope or language of any one or more of the appended claims. A

Particularly we wish to point out that in the annexed claims the references to aminoand hydroxy-pyridine, quinoline or isoquinoline are intended. to include also such radicals oi the kind specified as contain besides the amino or hydroxylgroup'also other usual substituents, for instance, alkyl and alkoxygroups and halogen atoms. However, as stated above, free acid substituents should not be'present.

This is a continuation in part of our copending application for Letters Patent Serial No. 702,427 fl16d December 14, 1933.

We claim: V g

1. d'-sulfonoamidebenzene-azo oz.cz'- diaminopyridine which forms inthe form 01 its hydrochloride red brown prisms melting at 266 C.

2. 4'- sulion'oamidebenzene-azooz.o:'- hydroxyaminopyridine which forms in the, form of its, hydrochloride light red crystals melting at 268 C.

3.. 4' -sulfonoamidebenzene-azo-6qaminoquinoline which forms in the form of its hydrochloride bright red crystals melting at 271C;

4. A20 compounds of the general formula:

area-s wherein the pyridine ring does not contain acid groups and the benzene ring containsno further substituents, n is one of the numbers 1 and 2' and whenn=1 the sulfamide group stands in para-position to the azo group andZ is a substituentselected from the group consisting of hydrogen, alkyl, 4- to 5-membered alkylene, mononuclear cycloalkyl, mononuclear arylalkyl,

- which azo compounds form water-soluble salts for a heterocyclic radical which is free from acid mononuclear cycloalkyl, mononuclear arylalkyl,

which azo compounds form water-soluble salts with mineral acids and caustic alkalies.

6. Azo compounds of the general formula:

N018 I I v wherein the 'benzene ring contains no further substituents, n is one of the numbers 1 and 2 and when n=1 thelsulfamide group stands in paraposition to the azo group,and Z is a substituent selected from the group consisting of hydrogen, alkyl, 4- to S-memberedallrylene, mononuclear, cycloalkyl, mononuclear aryalkyl, and R: stands groups and is seleetedfrom the group consisting of amino -pyridines, -quinolines and -isoquino lines, hydroxy-pyridines, hydroxy-isoquinolines,

hydroxye-quinoline, substituted hydroxy-quinolines wherein the substituents' are limited to monovalent none-cyclic substituents and the corresponding N -alk'ylated compounds, a nuclear carbon atom of which radical is directly con-l nected with the azo group, which azo compounds form water-soluble, salts with mineral acids and caustic alkalies.

7. Azo compounds of the general formula: 7

wherein the benzene ring not, contain further substituents, and R: stands for a heterocyclic radical containing nitrogen in basic linkage, which heterocyclic radical is iree from acid groups and sel'ected from the group consisting of amino. -pyridines, equinolines and -isoquinolines, hyd oxy-pyr dines. hyd oxydsoquino nes, hy-

droxy-q noli'ne, substituted hydroxy-quinolines tituents are limited to monovalentnon-cyclic substituents and the correwherein the subs sponding N.-alkylatedcompounds, .a nuclear carbon atom ,of which radical is directly connected with the am group andZ stands for a substituent selected from the "group consisting of hydrogen, alkyl, 4- to 5-.membered altylenasalts with mineral acids'and caustic alkalies.

mononuclear cycloalkyl, mononuclear arylalkyl,

which azo compounds form water-soluble salts with mineral acids and caustic alkalies.

8. Azo compounds of the general formula:

z Nels wherein the benzene ring contains no further substituents, n is one of the numbers 1 and 2 and when n=1 the sulfamide group stands in parapositionto the azo group, and Z is a substituent selected from the group consisting of hydrogen,

'alkyl, 4- 'to 5membered alkylene, mononuclear cycloalkyl, mononuclear arylalkyl, and wherein the pyridine ring does not contain acid groups, which azo compounls form water-soluble salts with mineral acids and caustic alkalies.

9. Azo compounds of the general formula:

substituents and Z stands for asubstituent selected from the group consisting of hydrogen, albl, 4-'to S-membered alkylene, mononuclear cycloalkyl, mononuclear arylalkyl, and wherein the pyridine ring does not contain acid groups which azo compounds form water-soluble salts with mineral acids and caustic alkalies; v 10. A20 compounds of the general formula:

wherein the benzene ring contains no'further substituents, n is one of the numbers 1 and 2.and

when n-' -1 the sulfamide group stands in paraposition to the azo group, and Z is a substituent selected from the group consisting of hydrogen,

alkyl, 4- to S-memhered alkylene, mononuclear cycloalkyl, mononuclear arylalkyl, and R2 stands wherein the benzene ring does not contain further for an aminoquinollne radical which is free from g acid groups and a nuclear carbon atom of which radical is directly connected with the azo group,- which azo compounds form water-soluble 'salts with mineral acids and caustic alkalies. -11. A20 compounds of the general formula:

wherein the benzene does not contain further subs'tituents and -Z stands for a 'substituent selected from the group consisting of hydrogen, 'allwl, 1- to 5-.membe1'ed alkylene, mononuclear cycloalkyl, mononuclear arylallryl, and R: stands for an amino-quinolineradical which :15 free from acid groups and a nuclear. carbon atom of which radical is directly connected with the azo; group, ,which azo compounds form water-soluble 

